Surface active quaternary higher dialkyl phosphonium salts

ABSTRACT

Higher dialkyl lower dialkyl phosphonium chloride salts, derived via quaternarization of phosphines with primary chlorides, have unexpected surfactant biocidal properties. Such quaternary salts are broad spectrum bactericides, fungicides and algicides, highly effective against gram negative organisms even in hard water. They are also useful as intermediates for the synthesis of quaternary phosphonium clays.

FIELD OF THE INVENTION

This invention is related to surface active quaternary phosphonium saltbiocides having two higher alkyl groups. One aspect of the inventionrelates to such salts, particularly to certain higher dialkyl lowerdialkyl phosphonium chlorides as novel compositions having unexpectedproperties. Another aspect relates to the use of such salts assurfactants and biocides having unexpected effectiveness in hard water.

PRIOR ART

Although surface activity and the biological properties of the varioustypes of quaternary higher alkyl ammonium salts were widely studied, thecorresponding phosphonium salts received little attention in the past asshown by the monograph on "Cationic Surfactants" by E. Jungermann whichwas published by M. Dekker, Inc. in New York, N.Y. in 1970. Knowledge isparticularly scarce about quaternary higher dialkyl phosphonium salts,especially the chlorides.

The primary disclosure on the latter compounds was made in U.S. Pat. No.3,230,069 by W. H. Preston, Jr., which makes an all-inclusive statementon plant growth inhibition by tetraalkyl phosphonium halides having C₁to C₁₆ substituents. This patent specifically discloses didodecyl andditetradecyl dimethyl-phosphonium chlorides:

    [(C.sub.12 H.sub.25).sub.2 P.sup.+(CH.sub.3).sub.2 ] Cl.sup.-

and

    [(C.sub.14 H.sub.29).sub.2 P.sup.+(CH.sub.3).sub.2 ] Cl.sup.-

However, Preston does not specifically dislcose the preparation orproperties of these compounds.

The only published preparation of a quaternary higher dialkylphosphonium salt is by H. R. Hays in an article which appeared in the"Journal of Organic Chemistry" in volume 31, on page 3819 in 1966. Haysdescribed the reaction of didodecyl phosphine with methyl iodide inmethanol yielding didodecyl dimethyl phosphonium iodide.

The surface activity and biocidal properties of quaternary highermonoalkyl phsophonium halide salts, in general, were disclosed in U.S.Pat. No. 3,281,365 by K. Moedritzer. This patent also makes anall-inclusive disclosure of such compounds with the general formula,##STR1## wherein R₁ is a C₆ to C₂₄ aliphatic group; R₂ to R₄ are C₁ toC₁₂ hydrocarbyl radicals and X is Cl, Br, I. However, Moedritzer doesnot specifically disclose any quaternary higher dialkyl phosphoniumsalt.

While work in the area of quaternary higher alkyl ammonium saltsresulted in the commercial development of a large number of cationicsurfactants and biocides no phosphonium salts were developed. In view ofthe increasing demands on the safety and effectiveness of such cationiccompounds, a systematic study, partly disclosed in the presentinvention, but not claimed, was started to synthesize novel quaternaryhigher alkyl phosphonium salts and to study their properties and uses.

In the present invention, it was found that certain novel surface activequaternary higher dialkyl phosphonium salts are particularly effectivebroad spectrum biocides and surfactants. For example, in contrast to thepreviously disclosed quaternary didodecyl dimethyl phosphonium chloride,the closely related but novel didecyl dimethyl phsophonium chloride isan outstanding biocide. Unlike the higher monoalkyl compounds ofMoedritzer, the present compounds are effective against gram negativebacteria and maintain their activity in hard water. Other novelcompounds, such as the dioctadecyl deithyl phosphonium chlorides areparticularly suitable intermediates for the preparation of tetraalkylphosphonium clay gelling agents described in our copending U.S. Pat.application, Ser. No. 402,465 filed on Oct. 1, 1973, now U.S. Pat. No.3,929,849.

SUMMARY OF THE INVENTION

Quaternarization of the appropriate secondary and/or tertiary aliphaticphosphines with primary alkyl chlorides at atmospheric pressure yieldshydrochloride complexes of the corresponding higher dialkyl phosphoniumchlorides. These complexes lose HCl in vacuo at elevated temperatures toyield the free phosphonium chloride salts. These salts have unexpectedsurfactant and biocide properties and as such, are surprisingly useful.They can be also be employed as intermediates for the synthesis of thecorresponding phosphonium clays.

PRODUCT COMPOSITIONS

The quaternary phosphonium salts, preferably chlorides, of the presentinvention have two higher alkyl and two lower alkyl substituents. Thepreferred compounds can be represented by the general formula:

    [R.sub.2 'P.sup.+R.sub.2 "] Cl.sup.- • (HCl).sub.x

    wherein R' is a C.sub.8 to C.sub.30 high and R" is a C.sub.1 to C.sub.4 low aliphatic hydrocarbyl radical selected from the group consisting of open chain alkyl, alkenyl and alkynyl radicals, x is 0 or 1. All the radicals are independently selected except that, in case the R' groups are dodecyl or tetradecyl and x is 0, the R" groups cannot both be methyl.

A more preferred group of compounds has the general formula:

    [(C.sub.r H.sub.2r.sub.+1).sub.2 P.sup.+(C.sub.s H.sub.2s.sub.+1).sub.2 ] Cl.sub.+• (HCl).sub.x

wherein r is 8 to 30, preferably 9 to 18; s is 1 to 4, preferably 2 to4, x is 0 or 1. The r and s values are independently selected, exceptthat in case of s being one and r being 12 to 14, x cannot be 0. Thesymbol r is more preferably either 9 or 11 or 16 to 18. It is preferredthat at least both of the higher alkyl radical substituents of the abovephsophonium chlorides should be primary alkyl groups. It is furthermorepreferred that the primary higher alkyl groups be straight chainmoieties. It is most preferred that at least one of the lower alkylgroups be primary isobutyl.

Particularly preferred compounds have the general formula:

    {[CH.sub.3 (CH.sub.2).sub.n ].sub.2 P.sup.+ (C.sub.s H.sub.2s.sub.+1).sub.2 }Cl.sup.-•(HCl).sub.x

wherein n is 15 to 17 and s is 1 to 4, preferably 2 to 4,

    {[CH.sub.3 (CH.sub.2).sub.m ].sub.2 P.sup.+(C.sub.s H.sub.2s.sub.+1).sub.2} Cl.sup.-•(HCl).sub.x

wherein m is 8 to 10, preferably 9, s is 1 to 4, preferably 1.

Among the unsymmetrical phosphonium compounds particularly preferred arethose of the formula: ##STR2## wherein the meaning of r and s is thesame as before and the specifically preferred meaning of s is 2.

Examples of phosphonium chlorides include those having the followingspecific quanternary phosphonium cation moieties: dioctyl dibutylphosphonium, dihexatriacontyl dimethyl phosphonium, ditriacontyl dietylphosphonium, dioctadecyl dipropyl phosphonium, docosyl dodecyldiisobutyl methyl phosphonium, dioctadecenyl dimethyl phosphonium,didocosyl dipropargyl phosphonium, octadecyl octadecenyl ethyl propargylphosphonium, didodecyl diisopropyl phosphonium, dihexadecyl diisobutylphosphonium, dioctadecyl dimethyk phosphonium, diundecyl diisobutylphosphoium, doctyl diisobutyl phosphonium, dioctyl ethyl isobutylphosphonium, didodecyl tertiary butyl methyl phosphonium, didecyldiisopropyl phosphonium, polysobutenyl dodecyl dimethyl phosphonium.

The phosphonium chloride compositions of the present invention haveunexpected surfactant and biological properties. These properties areinherent in the structure of these compositions, namely, the bonding oftwo higher and two lower aliphatic hydrocarbyl groups to thetetracovalent phosphorus. Similar phosphonium chloride compositionshaving one higher alkyl and one lower alkyl group per phosphorus do notexhibit comparable properties.

In view of the prior work on quanternary higher monoalkyl phosphoniumsalts, it was completely unexpected that the present quanternary higherdialkyl phosphonium salts of a well defined type of structure, fallingwithin the known broad, generic term tetraalkyl phosphonium chloride,would have unexpected and highly superior properties. In particular, itwas found that the present compounds have unique combinations ofunexpected properties: surfactancy, gelling ability, broad spectrumbactericidal-fungicidal-nematocidal action, high activity against gramnegative bacteria, hard water resistance and low mammalian toxicity.

The two higher dialkyl dimethyl phosphonium chlorides, i.e. thedidodecyl and ditetradecyl phosphonium compounds, previosly dislosed, donot possess the biological properties of the present compounds.

The hydrogen bonded hydrochloride complexes of the present quaternaryhigher dialkyl phosphonium chlorides are the primary products in theirpreparation. They are unexpectedly stable thermally, and exhibit thebiocidal properties of the free salts. It these complexes are subjectedto high temperatures at reduced pressures, they lose the hydrogenchloride. Such complexes of the formula:

    [R'.sub.2 P.sup.+R.sub.2 "] Cl.sup.-•HCl

and

[(C_(r) H_(2r) ₊₁)₂ p⁺(C_(s) H_(2s) ₊₁)₂ ] Cl⁻•HCl

are generally novel and can also be used as clay reactants.

PROCESS OF PRODUCT PREPARATION

The quaternary phosophonium compounds of the present invention areprepared from the corresponding secondary or tertiary aliphaticphosphines via atmospheric quaternarization by primary alkyl chlorides.The novel phosphine intermediates of the present products and theirquaternarization will be claimed separately. The general methods for thepreparation of the present products are the following.

Secondary, higher or lower dialkyl phosphines can be quaternarized withthe corresponding primary alkyl chlorides, e.g. ##STR3## The firstproducts of secondary phosphine (Ia and b) alkylation are thecorresponding tertiary phosphine hydrochlorides (IIa and B). These arenot accumulated in the reaction mixture, indicating their increasedreactivity for further alkylation. The first isolable products of thereaction sequence are the quaternary phosphonium chloride hudrochloridecomplexes (III). These complexes are stable under the usual conditionsat temperatures of about 80° to 200° C. However, when they are placedunder vacuum at these elevated temperatures they are converted to thefree quaternary salts, IV, on losing hydrogen chloride.

When starting with the higher dialkyl phosphine (Ia), the abovealkylations can be surprisingly carried out at atmospheric or relativelylow pressures, at up to 5 atmospheres, at temperatures above the boilingpoints of the lower alkyl chloride reactants. In such atmosphericalkylations, the lower alkyl chloride (R"Cl), preferably methylchloride, is introduced at approximately the reaction rate into thealkylating vessel, containing the phosphine. Such alkylations areespecially facile when methyl chloride is used.

The thermal stability of the novel phosphonium salts and their complexesis much higher than that of their ammonium analogs. Consequently,preferred high reaction temperatures in the range of 150° to 250° C canbe employed, dependent on the reactants, without significant productdecomposition. The high thermal stability usually allows one to operatewithout a solvent which otherwise would be needed to accelerate thereaction and/or to dissolve a product which is solid at lowertemperatures. Of course, solvents may be used. As solvents usually thoseare chosen which are known to accelerate S_(N) ² reactions and arestable under the extreme reaction conditions. For example, dimethylformamide is a preferred solvent.

The corresponding unsymmetrical trialkyl phosphines (Va and b) can alsobe used as starting materials for the production of the presentquaternary higher dialkyl phosphinium chlorides: ##STR4## This method isparticularly advantageous if the unsymmetrical phosphonium chlorides aredesired wherein the two R' and/or two R" groups are different.

The trialkyl phospines are more reactive towards the primary alkylchloride reactants than the secondary phosphines. Trialkyl phosphinealkylations with methyl chloride can be carried out at temperatures aslow as 80° C. In the case of the lower alkyl chloride reactants, thereactions again proceed at atmospheric or near atmospheric pressures upto 5 atmospheres at temperatures as high as 200° C. In general, thepreferred reaction temperature ranges from 80 to 200° C. In general, itis preferred to introduce the smallest alkyl substituent of the productvia the chloride reactant (R"Cl) of this scheme. Otherwise, thealkylation of tertiary phospines is similar to that of the secondaryphosphines. Gaseous reactants are introduced preferably at about theirrate of absorption. Solvents are again optional, the preferred solventbeing dimethyl formamide.

SURFACTANT AND BIOCIDAL COMPOSITIONS

As previously noted, the quaternary higher dialkyl lower dialkylphosphonium salts of this invention are useful as surfactants andbiocides. The preferred compounds can be represented by the generalformula:

    [R.sub.2 'P.sup.+R.sub.2 "] X.sup.-• (HX).sub.x

wherein R' is a C₈ to C₃₀, preferably C₉ to C₁₈, high aliphatic radicaland R" is a C₁ to C₄ low aliphatic hydrocarbyl radical, bothindependently selected from the group consisting of open chain alkyl,alkenyl and alkinyl radicals, X is an anion selected from the groupconsisting of negatively charged inorganic and organic nonradicalspecies. Such inorganic anions include halides such as chloride,bromide, fluoride; phosphates, such as polyphosphates; phosphite,sulfate tetrafluoroborate, nitrite and nitrate. Organic anions includecarboxylates, having 1 to 30, preferably 1 to 18, carbon atoms, such asacetate, benzoate neotridecanoate, ethylenediamine tetraacetate; organicphosphate, phosphonate and phosphite anions such as C₂ to C₆ dialkyldithiophosphate, phosphate, phosphite and phosphonate; C₁ to C₃₀hydrocarbon sulfonate such as methanesulfanote, benzenesulfonate,tetrapropylenesulfonate; C₁ to C₂₄, preferably C₁ to C₁₂ alkyl sulfatesuch as methylsulfate, docosylsulfate, the symbol x is 0 or 1,preferably 0.

Chloride anions are most preferred because of t the unexpected ease ofpreparation of the chloride salts and their surprisingly higheffectiveness. Finally x is 0 or 1, preferably 0.

A more preferred group of compounds has the general formula:

    [(C.sub.r H.sub.2r.sub.+1).sub.2 P.sup.+(C.sub.s H.sub.2s.sub.+1).sub.2 ] X.sub.+•(HX).sub.x

wherein r is 8 to 30, preferably 9 to 18; s is 1 to 4, preferably 2 to4; and X, x are the same as before. It is preferred that the higheralkyl substituents of the above phosphonium salt compounds should beprimary alkyl groups. It is furthermore preferred that the primaryhigher alkyl groups be straight chain moieties. It is particularlypreferred that at least one of the low alkyl groups be isobutyl.

The particularly preferred anions of the above surfactants and/orbiocides are chloride, fluoride, sulfate; alkyl sulfates, carboxylates,phosphates, phosponates, phosphites. Specifically preferred arechlorides and fluorides. Most preferred are chlorides.

The anion of the above salts may be free or hydrogen bonded with aprotic acid derived from the same or another anion.

The particularly preferred compounds to be used for producing clayderivatives have the general formula:

    {[CH.sub.3 (CH.sub.2).sub.n ].sub.2 P.sup.+(C.sub.s H.sub.2s.sub.+1).sub.2 } X.sup.-•(HX).sub.x

wherein n is 7 to 29, preferably 15 to 17 and s is 1 to 4, preferably 2to 4, and X, x are the same as before.

Another particular subgroup of compounds specially useful as biocides isof the formula:

    }[CH.sub.3 (CH.sub.2).sub.m ].sub.2 P.sup.+(C.sub.s H.sub.2s.sub.+1).sub.2 } X.sup.-•(HX).sub.x

wherein m is 7 to 29, preferably 8 to 18, more preferably 9 to 10, s is1 to 4, preferably 1, 2, 4 and X, x are the same as before.

Among the unsymmetrical compounds are particularly preferred, both asbiocides and surfactants, those of the formula: ##STR5## wherein themeaning of r, s and X, x are the same as before for the preferredcompounds.

As it will be shown by examples, the surfactant compositions of thepresent invention are surprisingly effective in reducing liquid to gas,particularly water to air, surface tension when employed in lowconcentrations ranging from 0.5 to 0.0001, preferably 0.1 to 0.001%.These compositions are particularly effective in reducing liquid toliquid, particularly water to organic liquid, specifically hydrocarbon,interfacial tension. In these latter applications, concentrationsranging from 0.5 to 0.00001, preferably 0.01 to 0.0001% may be used.Similarly, these surfactants may be used for reducing the interfacialtension among liquids and solids and as such may have a detergentaction. In the various applications based on the surfactant propertiesof our phosphonium compounds the concentration depends on theeffectiveness in the particular practical system. In contrast tolaboratory systems consisting of pure known components, othercomponents, such as impurities, different natural and syntheticsurfactants, are likely to be present in commercial use. In general, theeffective concentration of the present higher dialkyl phosphoniumcompounds is surprisingly lower than that of the related highermonoalkyl phosphonium compounds. The effectiveness of the presentphosphonium surfactants is particularly surprising in reducinginterfacial tension.

Typical surfactant applications, such as detergent, flotation,emulsification uses, are reviewed by E. Jungermann in a mongraphentitled "Cationic Surfactants", which was published by M. Dekker, Inc.in 1970 in New York, N.Y. This review shows that these applications arecommercial for ammonium cationics but unknown for the presentphosphonium compounds as noted on page 197 of the monograph.

The biocidal effect of the present quaternary higher dialkyl phosphoniumsalts is primarily exhibited against organisms selected from the groupconsisting of Protophyta, Thallophyta, viruses and invertebrates.

The biocidal, preferably microbiocidal, compositions of the presentinvention are unique, compared to the known quaternary phosphonium saltsbecause of their activity against gram negative bacteria, particularlythe Pseudomonancae family, Pseudomonas genus, Pseudomonas aeruginosaspecies. Furthermore, they are unique in their ability to maintain thisbactericidal effectiveness in hard water. They are also surprising inhaving a broad microbiocidal spectrum, i.e. activity.

The microbiocidal activity of the present compositions is unexpectedlybroad. It includes primitive plants, Protophyta; algae, molds andyeasts, Thallophyta. Among the primitive plants, unexpected activity isobserved against bacterial organisms, Schyzomycetes class and bluegreenalgae, Schyzophycae class. The bacterial organisms are defined inBergey's "Manual of Determinative Bacteriology", published by theWilliams and Wilkins Co., Seventh Edition, Baltimore, Md., 1957.

The present compounds are highly active against gram positive organismssuch as Streptococcus pyogenes, important in sanitation; Staphylococcusaureus which is important, e.g., in the cosmetics field; Bacillusmycoides, significant in slime formation. High activity against gramnegative organisms includes, for example, Escherichia coli andSalmonella typhosa, important in the sanitation field; Aerobacteraerogenes, often involved in slime formation; Pseudomonas stutzeri,frequently attacking cosmetics, and other Pseudomonas species, attackingcrude and fuel oils. High activity is also observed against acid fastbacteria such as Mycobacterium tuberculosis.

The present compositions are unexpectedly effective against Thallophyta,namely the yeasts and yeast-like fungi and molds and mold-like fungi.These fungal organisms, when involved in attacking industrial products,are often designated as mildew. Among the medical monilias which arecontrolled by the present compositions, is the yeastlike Candidaalbicans, important in several human infections, e.g. thrush, vaginitisand fingernail infections. High activity is also observed against moldtype fungi important in aspergillosis and dermatophytosis. For example,Aspergillus fumigatus important in pulmonary diseases, and Trychophytoninterdigitale, important in foot infections, are controlled.

The various classes of fungi which can be controlled by the presentcompositions are listed on pages 163 to 166 in the "Handbook ofMicrobiology" by M. B. Jacobs and M. J. Gerstein, which was published bythe Van Nostrand Reinhold Co. in New York, N.Y., 1960. The medicallyimportant fungi controlled by the present compositions are discussed inChapter 32 of the "Textbook of Microbiology" by W. Burrows, which waspublished by the W. Saunders Co., in Philadelphia, Pa., 1959.

The antiviral activity of the present compounds is to be also includedamong their microbiocidal effects. As far as the broader biocidaleffects are concerned, it is noted that the present compositions areactive against invertebrates such as Culex quinquefasciatus; the larvaeof mosquitoes, Aedes aegypti; worms and molluscs.

As far as the activity against molds and yeasts is concerned, itincludes mildew causing fungi, such as Penicillium glaucum, Penicilliumluteum, Penicillium funiculosum, Aspergillus flavus, Aspergillus oryzae,Chaetomium globosum, Trichoderma viride and Pullularia pullulans.Activity against these fungal organisms is important for industrialbiocides, i.e. mildewcides. Other fungal organisms, important inagriculture and oil products, are also controlled by the presentcompositions.

The algae and protozoa, which are surprisingly controlled by the presentproducts, include the Eurocaryotic algae such as the brown and redalgae. Specific exemplary organisms are Chlorella pyrenoidosa andChlorella vulgaris. The Eurocaryotic algae are reviewed on page 102 ofthe "Microbial World" by R. V. Stanier, M. Doudoroff and E. A. Adelberg,published by Prentice-Hall, Inc., Englewood Cliffs, N.J., 1963.

The exact degree of activity of the present microbiocides is, of course,dependent on their chemical structure, the microorganism involved, andon the other components of the environment, i.e. biosystem. For example,in aqueous media, the water hardness usually has an adverse effect onthe effectiveness of the microbiocide. Cationic, anionic, and nonionicsurfactants and proteins may also interfere with the activity. Othercomponents of detergents may also have an effect.

The above considerations are discussed in detail in Chapter 14 on the"Germicidal Properties of Cationic Surfactants" of the earlier referredJungermann monograph.

The effectiveness of the present compositions particularly depends ontheir chemical structure when used against organisms of the genusPseudomonas such as Pseudomonas aeruginosa. For example, in the case ofhigher dialkyl dimethyl phosphonium chlorides, only compounds of di-C₉to C₁₁ -alkyl substitution are active against these organisms. In thecase of the i-butyl substituted quaternary higher dialkyl phosphoniumsalts, a high level of effectiveness is exhibited by compoundsregardless of the exact length of the higher alkyl groups.

The higher dialkyl phosphonium compounds in general exhibit decreasedmammalian oral toxicities as the alkyl chain length increases. Nontoxiccompounds of surprising microbiocidal effectiveness were obtained whenthe number carbon of the n-alkyl chains was 16 or higher per chain.

Microbiocidal activity of known quaternary salts is particularlyunsatisfactory in hard water against certain gram negative bacteria suchas Escherichia coli. The compounds of the present invention aresurprisingly effective in such cases.

Obviously, the selection of a single, surface active microbiocide of thepresent invention or a combination of microbiocides and surfactantsinvolving at least one of the present compounds depends on the exactnature of the application. This selection is greatly facilitated forpersons trained in the art by the surprising generic and subgenericproperties of the present compositions and alows them to use moreeffective formulations, which are for example, useful as detergentantiseptics, disinfectants, by having the present compounds asconstituents in effective amounts.

The present invention provides compositions of increased surfactancy andincreased biocidal properties containing as a minor component, thequaternary higher dialkyl lower dialkyl salts of the present invention,in amounts sufficient to provide said surface active and biocidalproperties in said compositions. According to the present invention,compositions are also provided which have either increased surfactancyor increased biocidal properties. Furthermore, compositions are providedwhich have increased biocidal properties against certain classes, geniand specii of organisms. Under biocidal properties, both the killing oforganisms and the inhibition of their growth are included. More specificphosphonium salt components can be preferred as disclosed earlier.

The major components of liquid and/or solid systems, wherein the presentbiocides are used, are well known in the prior art. For example, thesystems where fungicides are used are described in Volume I on Chapters6 to 11 of a monograph "Fungicides" edited by D. C. Torgeson andpublished by Academic Press, Inc., New York, N.Y., 1967. Particularly,Chapter 6 discusses the various types of formulations: dusts, e.g.kaolinite, calcium carbonate; water dispersible powders, emulsions andsolutions. Chapters 7 to 9 describe the various agriculturalapplications such as foliar, seed and soil treatments and post-harvestuses for preserving crops. Chapter 10 enumerates the main industrialpreservative applications involving textiles, paper and pulp, rubber,plastics and paint, electrical and electronic equipment, petroleumproducts, leather, drugs and cosmetic preservatives. Finally, Chapter 11is on wood preservatives. Similarly, various formulations are used inthe bactericidal and algicidal field. However, in the bactericidalfield, usually living organisms are protected from pathogenic bacteria.Consequently, in this field, biocides are mainly used to fight bacterialinfections and to preserve drugs and cosmetics. The major medium ofaction for bactericides is therefore water and organic liquids,preferably solvents such as hydrocarbons, e.g. paraffins and alcohols,e.g. hexadecyl alcohol; esters, e.g. glycerides. In the case ofalgicides, of course, water medium is involved. Accordingly, the majorcomponent of the present biocidal compositions is selected from thegroup consisting of water, organic solvents, powders, elastomers,plastics, textiles, leather, cosmetics, drugs, petroleum products.

In some cases, the present higher dialkyl lower dialkyl phosphoniumsalts are used in minor amounts for the sole purpose of increasingsurface activity. The major amount of the compositions is preferablyselected from the group consisting of water and organic liquids. For thereduction of surface tension, the present compounds are preferablyemployed in water. Applications for the reductions of interfacialtension preferably involve water and hydrocarbon liquids.

In the same maner, a method of changing the surface and biocidalproperties of compositions by applying thereto minor amounts of aquaternary phosphonium salt, having two higher alkyl and two lower alkylsubstituents, in effective amounts, is provided. Such a method can bespecially directed to reduce the surface tension of a composition.Another specific feature of the invention, is a method reducing theinterfacial tension of normally immersible compositions. A further partis a method of inhibiting in their habitat, the growth of organisms asspecified previously. Finally, a method of killing organisms previouslydescribed comprising applying to their habitat, minor amounts of saidquaternary phosphonium salts in effective amounts is provided.

EXAMPLES A. Syntheses (1 - 8)

The structures of the eight quaternary higher dialkyl phosphoniumchlorides, whose synthesis will be illustrated with examples, are shownwith their melting range and elemental composition in Table I. Thislisting of compounds in the Table is in the order of their increasingmolecular weight. The description of their preparation in examples,however, is arranged according to the chemistry involved. In general,the conversions were complete and the yields were quantitative. Lossesdependent on the solvents used, occurred on recrystallization.

a. Quaternarization of Secondary Phosphines (1 - 4)

In the first four examples, the quaternarization of higher di-n-alkylphosphines with methyl chloride is illustrated. The first two of theseexamples also describe the primary quaternary phosphonium chloride -hydrogen chloride complexes of such reactions and their conversion tothe corresponding free salts, which can be followed via the downfieldchemical shift of the α-methyl doublet signals.

b. Quaternarization of Tertiary Phosphines (5-8)

The second group of four examples describes the quaternarization oftrialkyl phosphines. The first three examples of this group show thequaternarization of higher di-n-alkyl lower monoalkyl phosphines withlower alkyl chlorides. The last example illustrates the other approachstarting with a higher mono-n-alkyl lower dialkyl phosphine and a highern-alkyl chloride.

                                      TABLE I                                     __________________________________________________________________________    Some Physical and Analytical Data of Quaternary Higher Dialkyl                Phosphonium Chlorides                                                                                Melting                                                                            Elemental Composition, %                          Sequence                                                                           Structure of      Range,                                                                             Calculated       Found                            No.  Phosphonium Cation                                                                              ° C                                                                         C    H   P  Cl   C    H    P  Cl                  __________________________________________________________________________    1    (C.sub.8 H.sub.17).sub.2 P.sup.+(CH.sub.3).sub.2                                                128-134.sup.a                                                                      66.95                                                                              12.49                                                                             9.59                                                                             10.97                                                                             68.54 12.45                                                                              9.61                                                                             10.83               2    (C.sub.8 H.sub.17).sub.2 P.sup.+(CH.sub.3)C.sub.2 H.sub.5                                       104-108.sup.a                                                                      67.73                                                                              12.56                                                                             9.19                                                                             10.52                                                                             67.33 12.22                                                                              9.07                                                                             10.22               3    (C.sub.9 H.sub.19).sub.2 P.sup.+(CH.sub.3).sub.2                                                165-168.sup.a                                                                      68.44                                                                              12.64                                                                             8.82                                                                             10.10             10.06               4    (C.sub.10 H.sub.21).sub.2 P.sup.+(CH.sub.3).sub.2                                               172-176.sup.a                                                                      69.71                                                                              12.77                                                                             8.17                                                                             9.35                                                                              69.73 12.91                                                                              8.19                                                                             9.37                5    (C.sub.12 H.sub.25).sub.2 P.sup.+(CH.sub.3).sub.2                                               127-132.sup.b                                                                      71.77                                                                              12.98                                                                             7.11                                                                             8.14                                                                              70.65 12.48                                                                              7.16                                                                             8.81                6    (C.sub.12 H.sub.25).sub.2 P.sup.+(C.sub.2 H.sub.5)CH.sub.                     2 CH(CH.sub.3).sub.2                                                                            53-56.sup.a                                                                        73.35                                                                              13.13                                                                             6.30                                                                             7.22                                                                              73.31 13.51                                                                              6.29                                                                             6.95                7    (C.sub.16 H.sub.33).sub.2 P.sup.+(C.sub.2 H.sub.5)CH.sub.2 CH(CH.sub.         3).sub.2          60-67.sup.b                                                                        75.63                                                                              13.36                                                                             5.13                                                                             5.88                                                                              75.16 13.42                                                                              5.07                                                                             6.57                8    (C.sub.18 H.sub.37).sub.2 P.sup.+(C.sub.2 H.sub.5).sub.2                                        80-83.sup.b                                                                        76.08                                                                              13.41                                                                             4.90                                                                             5.61                                                                              76.65 13.72                                                                              5.09                                                                             5.56                __________________________________________________________________________     .sup.a Crude product after removal of volatiles.                              .sup.b Recrystallized.                                                   

EXAMPLE 1 - Didodecyl Dimethyl Phosphonium Chloride

Into a Pyrex glass cylindrical reaction vessel, equipped with a Teflonneedle valve and a magnetic stirrer, were placed 18.05 g (0.05m) ofdidodecyl phosphine reactant and 4.1 g (0.1m) of acetonitrile solvent.The vessel was then cooled by dry ice, and evacuated. Thereafter, 6.4 g(0.126m) of methyl chloride reactant was condensed into the vessel. Thevessel was then closed and heated with stirring to 80° C in 35 minutesand kept there for 5 hours.

The didodecyl phosphine was not miscible with the acetonitrile. However,on heating the mixture at 80° C, a homogeneous liquid mixture resultedin 10 minutes. After 5 hours at 80°, the nuclear magnetic resonancespectrum of a sample indicated an essentially complete quaternarization,by exhibiting the expected intensity of the protons on the carbons nextto the phosphonium moiety, particularly a methyl doublet at 2.0 ppm.

The crude reaction mixture was then evacuated to 100 mm at ambienttemperature to remove the methyl chloride. A subsequent phosphorus andchlorine analysis and the nmr chemical shift of the doublet signal ofthe α-methyl groups of the residual product (at 2.05 ppm from TMS withcoupling constant, J_(P-C) = 14 cps) indicated that the resultingquaternary phosphonium chloride was in the form of a hydrochloridecomplex.

The residual product was heated to 100° C at 0.2 mm for 90 minutes toremove all the acetonitrile. The solvent-free residue was dissolved inan equal amount of refluxing toluene. The position of the methyl doubletat 2.38 ppm in the nmr spectrum of the resulting solution indicated thata significant portion of the salt was still in the complex form. Oncooling to -20° C, crystallization of most of the product from tolueneoccurred. On filtration by suction in a nitrogen box, 12g (73%) of thefree salt, exhibiting an nmr methyl doublet at 2.53 ppm with a J_(P-C)of 14.5 ppm in benzene was obtained.

EXAMPLE 2 - Dinonyl Dimethyl Phosphonium Chloride

Into a cyclindrical vessel, equipped with a sintered glass gas inductor,in and out bubblers, and a magnetic stirrer, is placed 2.83 g (0.1m) ofdinonyl phosphine under nitrogen. The stirred phosphine is then heatedto 120° C and kept at that temperature while methyl chloride wasintroduced into it at a rate sightly greater than its absorption. After6 hours at 180° C, a weight gain of 8.5 g was observed. An additionalseven hours resulted in 0.5 g more weight gain, which was determinedafter purging any dissolved methyl chloride with nitrogen. A completequaternarization of the dinonyl phosphine by methyl chloride to form thehydrochloride complex of the desired quaternary phosphonium chlorideshould have resulted in a total of 10.1 g weight gain.

The crude complex reaction product solidified to a gel-like substance atroom temperature. Most of it was melted, poured into a distilling flaskand heated with nitrogen capillary bubbling at 200° in high vacuo toremove all volatiles. By the end of the heating, the vacuum improvedfrom 0.5 to 0.005 mm. No dinonyl phosphine was recovered in thereceiver, indicating its complete quaternarization. The less thantheoretical weight of the crude complex was due to a partial loss of HClduring the reaction. The subsequent heating in vacuo resulted in acomplete HCl loss and a quantitative yield of the free salt as aresidual product. This sequence of reactions is supported by the nmrspectra of samples. The partially decomposed complex in deuterobenzeneexhibited an α-methyl doublet at a chemical shift value of 2.33 ppm(J_(P-C) 14 cps). In the free salt, this signal shifted downfield, as inthe previous example, to 2.63 ppm (J_(P-C) 15 cps).

EXAMPLE 3 - Didecyl Dimethyl Phosphonium Chloride

In the manner described in the previous example, 31.4g (0.1 m) ofdidecyl phosphine was reacted with methyl chloride at 180° C for 8hours. A complete quaternarization and a partial dissociation of theprimary complex product were observed again. On subsequent heating at200° under 0.15 mm for 3 hours, the expected free quaternary phosphoniumchloride was obtained in a quantitative yield. This product solidifiesto form a colorless, waxy solid at room temperature. Its nmr spectrumexhibits a characteristic doublet for the α-methyl protons at 2.62 ppm(J_(P-C) 15 cps).

EXAMPLE 4 - Dioctyl Dimethyl Phosphonium Chloride

As described in the previous two examples, 25.8 g (0.1 m) of dioctylphosphine was reacted with methyl chloride at 180° C for 6 hours to forma mixture of the desired quaternary phosphonium chloride and itshydrochloride complex. Subsequent heating, at 200° under 0.4 mm for 3hours provided the free salt in a 97% yield as a colorless waxy solid atroom temperature. The characteristic α-methyl doublet of this product indeuterobenzene appears at 2.58 ppm (J_(P-C) 15 cps).

EXAMPLE 5 - Dioctyl Ethyl Methyl Phosphonium Chloride

Into 14.4 g (0.5m) of dioctyl ethyl phosphine, placed in the bubblerreactor described in Example 2, methyl chloride was introduced at 130° Cfor 4 hours. The degree of weight gain observed corresponded to aquantitative formation of the desired product; a colorless, waxy solidat room temperature. In the nmr spectrum of this product, the α-methyldoublet appears at 1.93 ppm (J_(P-C) 14 cps).

The product is highly soluble in toluene even at low temperatures. It isprecipitated from toluene by n-heptane.

EXAMPLE 6 - Didodecyl Isobutyl Ethyl Phosphonium Chloride

Into the bubbler reactor of Example 2, 34.2 g (0.1 m) of didodecylprimary isobutyl phosphine was placed under nitrogen. Then ethylchloride was introduced in the usual manner at 200° for 15 hours to formthe desired quaternary chloride in a quantitative yield. The product isa colorless solid at room temperature. It is highly soluble in toluene.

EXAMPLE 7 - Dihexadecyl Isobutyl Ethyl Phosphonium Chloride

In the manner described in the previous example, 27 g (0.05 m) ofdihexadecyl primary isobutyl phosphone was quantitatively reacted withethyl chloride at 200° C in 12 hours. The amount of ethyl chlorideabsorbed indicated that the reaction was already essentially complete in6 hours. Most of the quaternary chloride product, 30g, a colorless solidat room temperature, was recrystallized from 100 ml hot n-heptane.Crystallization started at room temperature. The mixture wasnevertheless cooled to -25° and filtered cold under nitrogen withsuction. After drying in vacuo, 26.5 g (88%) of recrystallized productwas obtained.

EXAMPLE 8 - Dioctadecyl Diethyl Phosphonium Chloride

In the first experiment, a magnetically stirred mixture of 8.5 g (0.25m)octadecyl diethyl phosphine and 7.2g (0.25m) octadecyl chloride washeated in a cylindrical reaction vessel under nitrogen at 190° for 24hours. The absence of the chloromethyl nmr triplet signal, in a sampleof the mixture after 3 hours, indicated that most of the conversionoccurred during the first few hours. The crude product was a colorlesssolid at room temperature and exhibited the expected nmr spectrum. Itwas recrystallized from 50 ml hot methyl ethyl ketone. After filtrationand rinsing at room temperature, the recrystallized product was dried at0.2 mm at ambient temperature. The yield of the dry purified product was75%.

In the second experiment, 342 g (1m) of the octadecyl diethyl phosphinereactant was added during the course of 80 minutes to 289g (1m) of thestirred nitrogenated octadecyl chloride at 190°. Heating of the reactionmixture was continued for 3 hours after the completion of the addition.Thereafter, the mixture was allowed to cool to 140' and at thattemperature methyl chloride was introduced into it to quaternarize anytraces of unreacted phosphine. The resulting crude product was thenrecrystallized from 1200 ml of methyl ethyl ketone to yield 587g (93%)of the desired purified quaternary phosphonium chloride.

B. Surfactant Tests (9)

To obtain standard data for estimating the surface activity ofquaternary higher dialkyl phosphonium salts, the surface tensions oftheir water solutions and the interfacial tensions of theirequilibriated solutions in water and a paraffinic hydrocarbon weredetermined as described by ASTM D-971-50.

EXAMPLE 9 - Effectiveness in Reducing Surface and Interfacial Tension

Didodecyl dimethyl phosphonium chloride and, for comparison, octadecyltrimethyl phosphonium chloride were tested as described above, accordingto ASTM D-971. The surface tension towards air measurement useddistilled water at 25°, which gives a base value of 72 dynes per cm. Forinterfacial tension measurements a water-paraffin (Nujol) system wasused. Without any added surfactant, this has an interfacial tension of52 dynes per cm. The interfacial tension measurements of the phosphoniumchloride solutions were made after equal volumes of the two immiscibleinstead and the given amount of salt were slowly stirred for 30 minutesto arrive at equilibrium concentrations of the salt. The data are shownin Table II.

The tension data show that the quaternary higher dialkyl compound is amuch more effective surfactant than the corresponding monoalkylderivative. It is effective in reducing both surface tension andinterfacial tension when present at a concentration of 0.001%. Incontrast, the monoalkyl compound is relatively ineffective even at ahundred times greater concentration. In comparison to all knownsurfactants, the ability of the quaternary higher dialkyl phosphoniumsalts is particularly outstanding in reducing interfacial tension.

C. Biocidal Tests

In the primary biocidal testing of the quaternary higher dialkylphosphonium salts, broth dilution was used as the primary method todetermine the minimum salt concentrations necessary for completeinhibition of bacterial, fungal and algal growth. Typically, 2 ml pertube of trypticase soy broth was used as nutrient medium. Usually 10 mgof the phosphonium chloride was dissolved in 5 ml ethanol and this wasthen diluted to 10 ml with water to give an aqueous ethanol stocksolution of 2000 ppm concentration.

                                      TABLE II                                    __________________________________________________________________________    Surface Activity of a Quaternary Higher Dialkyl Phosphonium Chloride          Versus the Corresponding Higher Monoalkyl Derivative                          Chemical Structure                                                            of the Cation of the                                                                     Tension Data, Dynes/cm, at 25°                              Quaternary Chloride                                                                      (at Various Salt Concentrations, %)                                __________________________________________________________________________               Surface Tension of Water                                                      (0.100)                                                                             (0.010)                                                                             (0.0075)                                                                            (0.005)                                                                             (0.0025)                                                                            (0.001)                              (C.sub.12 H.sub.25).sub.2 P.sup.+(CH.sub.3).sub.2                                        29    31    31    32    33    33                                   C.sub.18 H.sub.137 P.sup.+(CH.sub.3).sub.3                                               41    42    --    --    --    --                                              Interfacial Tension of Water-Nujol                                            (0.100)                                                                             (0.010)                                                                             (0.0075)                                                                            (0.005)                                                                             (0.0025)                                                                            (0.001)                              (C.sub.12 H.sub.25).sub.2 P.sup.+(CH.sub.3).sub.2                                         2     3    3     3     3     3                                    C.sub.18 H.sub.37 P.sup.+(CH.sub.3).sub.3                                                10    12    --    --    --    --                                   __________________________________________________________________________

The inoculum of the microorganism was one drop of a thousand folddiluted 24 hour culture which usually contained 1000 bacteria or 10,000fungal or algal cells. To the inoculated broth media, different amountsof the experimental chemicals were administered. The media were thanobserved for visible growth after a period dependent on the type of themicroorganism used. Bacterial growth or inhibition was observed afterone or two days. Growths of fungi and algae were checked after 7 or 14days. When observing a series of dilutions of the experimental chemical,minimum growth inhibitory, i.e., microbiostatic, concentrations (MIC)were determined. EXAMPLE 10 - ACTIVITY AGAINST GROWTH OF REPRESENTATIVEBACTERIA, FUNGI AND ALGAE

A number of quaternary phosphoinium chlorides characterized in Table Iwere broth dilution tested against an important gram negative bacterialorganism, Pseudomonas aeruginosa; a common gram positive bacterium,Staphylococcus aureus, and a widespread fungus, Aspergillus niger, and acommon algal organism, Chlorella vulgaris. The test results are shown inTable III.

The results indicate striking differences in the activity of the variousphosphonium chlorides against the most difficult to control organism,Pseudomonas aeruginosa. Against this species of the Pseudomonas genus,the known didodecyl dimethyl phosphonium chloride (Seq. No. 4) shows nosignificant activity. As it is indicated by their much lower minimuminhibitory concentrations, the activity of the novel quaternary higherdialkyl phosphonium salts is much higher. Particularly outstanding intheir activity are didecyl dimethyl phosphonium chloride (Seq. No. 3),didodecyl and dihexadecyl isobutyl ethyl phosphonium chlorides (Seq.Nos. 6 and 7).

                                      TABLE III                                   __________________________________________________________________________    Microbiocidal Activity of Quaternary Higher Dialkyl Phosphonium               Chlorides Against Representative Bacteria, Fungi and Algae                                                Minimum Inhibitory Concentration,ppm (After                                   Days)                                                                         Pseudo-                                                                             Staphylo-                                   Sequence                                                                           (Example                                                                           Structure of      monas coccus                                                                              Aspergillus                                                                          Chlorella                      Number                                                                             Number)                                                                            Phosphonium Cation                                                                              aeruginosa                                                                          aureus                                                                              niger  vulgaris                       __________________________________________________________________________    1    (4)  (C.sub.8 H.sub.17).sub.2 P.sup.+(CH.sub.3).sub.2                                                250(1)                                                                              0.5(2)                                                                              7.5(14)                                                                              4(14)                          2    (5)  (C.sub.8 H.sub.17).sub.2 P.sup.+(CH.sub.3)C.sub.2 H.sub.5                                       250(2)                                            3    (3)  (C.sub.10 H.sub.21).sub.2 P.sup.+(CH.sub.3).sub.2                                               16(1) 0.5(2)                                                                              0.25(14)                                                                             0.125(14)                      4    (1)  (C.sub.12 H.sub.25).sub.2 P.sup.+(CH.sub.3).sub.2                                               2500(1)                                                                             1.0(1)                                                                              75(7)  8(7)                           5    (6)  (C.sub.12 H.sub.25).sub.2 P.sup.+(C.sub.2 H.sub.5)CH.sub.2                    CH(CH.sub.3).sub.2                                                                              16(1) 0.5(1)                                                                              1.0(14)                                                                              0.5(14)                        6    (7)  (C.sub.16 H.sub.33).sub.2 P.sup.+(C.sub.2 H.sub.5)CH.sub.2                    CH(CH.sub.3).sub.2                                                                              16(1) 0.5(1)                                                                              0.5(14)                                                                              0.5(14)                        7    (8)  (C.sub.18 H.sub.37).sub.2 P.sup.+(C.sub.2 H.sub.5).sub.2                                        500(2)                                                                              15(2) 15(14) 7.5(14)                        __________________________________________________________________________

The biocidal activity differences are also clearly shown on the fungus,Aspergillus niger. Against this organism, the minimum inhibitoryconcentration of the novel didecyl dimethyl phosphonium chloride (Seq.No. 3) was three hundred times smaller than that of the known didodecyldimethyl phosphonium chloride (Seq. No. 4).

The same trend of activities are observed against the alga, Chlorellavulgaris and the gram positive bacterium, Staphylococcus aureus.However, these organisms show much less structure specificity in theirresponse to the various quaternary phosphonium chlorides. EXAMPLE 11 -MICROBIOCIDAL SPECTRUM OF DIDECYL DIMETHYL PHOSPHONIUM CHLORIDE

To test the breadth of the microbiocidal spectrum of didecyl dimethylphosphonium chloride, minimum inhibitory concentrations (MIC's) weredetermined against several additional organisms in broth dilution testswith the following results:

Against gram negative bacterial organisms, important in sanitation, i.e.Escherichia coli and Salmonella typhosa, the MIC's were 0.5 and 8 ppm,respectively. Against the yeast-like fungus, Candida albicans, importantin thrush, vaginitis and other human infections, the MIC found was 0.25ppm.

EXAMPLE 12 - BACTERICIDAL EFFECTIVENESS IN HARD WATER

To determine the effectiveness of a quaternary higher dialkylphosphonium salt, i.e. didecyl dimethyl phosphonium chloride as abactericide, the AOAC Germicidal and Santitizer Test was used. Theresults are shown by Table IV. The high kill by the higher dialkylcompound of the bacteria in the soft, distilled water and a simikill inthe hard water shows a bactericidal effect which is surprisinglyinsensitive the water.

                                      TABLE IV                                    __________________________________________________________________________    Bactericidal Activity in Distilled and Hard Water of a Quaternary             Higher Dialkyl Phosphonium Chloride Versus a Higher                           Monalkyl Derivative both at a Concentration of 25 ppm                         __________________________________________________________________________                         Reduction of Live Organisms                              Chemical Structure                                                                        Bacterial                                                         of the Cation of the                                                                      Micro-   In Distilled                                                                          of 200 ppm                                       Quaternary Chloride                                                                       organism Water   Hardness                                         __________________________________________________________________________    (C.sub.10 H.sub.21).sub.2 P.sup.+(CH.sub.3).sub.2                                         Staph. aureus                                                                          99.999  99.999                                                        E. coli 99.999  99.900                                           C.sub.20 H.sub.41 P.sup.+(CH.sub.3).sub.3                                                 Staph. aureus                                                                          99.999  92                                                            E. coli 99.999  61                                               __________________________________________________________________________

In contrast the activity of the highly effective higher monoalkylcompound is drastically reduced when employed in hard water.

EXAMPLE 13 - TOXICITY TOWARDS MAMMALS

The acute oral toxicity of didecyl dimethyl phosphonium chloride anddioctadecyl diethyl phosphonium chloride was determined using Swissalbino mice. The median lethal toxicities found were 350 and 2840 mgsalt per body kg mice, respectively. This means a medium level of oraltoxicity for the didecyl compound and an essential lack of oral toxicityfor the dioctadecyl compound. Due to its lack of toxicity the lattercompound, although not highly active microbiocidally, appearssurprisingly attractive for some fungicidal applications.

What is claimed is:
 1. Quaternary phosphonium chlorides of the formula:

    [R.sub.2 'P.sup.+R.sub.2 "] Cl.sup.- • (HCl).sub.x

wherein R' is a C₈ to C₃₀ high open chain alkyl, and R" is a C₁ to C₄low aliphatic hydrocarbyl group selected from the group consisting ofopen chain alkyl, alkenyl and alkinyl groups, x is 0 or 1; all thegroups being independently selected, except, that in case the R' groupsare dodecyl or tetradecyl and x is 0, the R" groups cannot both bemethyl.
 2. Quaternary higher dialkyl lower dialkyl phosphonium chlorideshaving the formula:

    [(C.sub.r H.sub.2r.sub.+1).sub.2 P.sup.+ (C.sub.s H.sub.2s.sub.+1).sub.2 ] Cl.sup.- • (HCl).sub.x

wherein r is 8 to 30, s is 1 to 4, x is 0 or 1, except that if r is 12to 14 and s is 1, x cannot be
 0. 3. A composition of increased surfaceactivity containing as a minor component a surface active quaternaryhigher dialkyl lower dialkyl phosphonium salt of the formula:

    [R.sub.2 ' P.sup.+R.sub.2 "] X.sup.- • (HX).sub.x

wherein R' is a C₈ to C₃₀ high alkyl group, R" is a C₁ to C₄ lowaliphatic hydrocarbyl independently selected from the group consistingof open chain alkyl, alkenyl and alkinyl, X is an anion selected fromthe group consisting of halides, phosphates, phosphites, sulfates,tetrafluoroborate, nitrites, nitrates, C₁ -C₃₀ carboxylates, organicphosphates, phosphonates, phosphites, C₁ to C₃₀ hydrocarbon sulfonatesand C₁ -C₂₄ alkyl sulfates, and x is 0 or 1; in effective surfactantamounts the major component being selected from the group of water andorganic liquids.
 4. Compounds according to claim 2, wherein r is 9 to11, s is 1 to 4 and x is 0 or
 1. 5. Compounds according to claim 2,wherein r is 16 to 18, s is 1 to 4 and x is 0 or
 1. 6. Quaternary higherdi-n-alkyl lower dialkyl phosphonium chlorides having the formula:

    [(CH.sub. 3 (CH.sub.2).sub.n ].sub.2 P.sup.+(C.sub.s H.sub.2s.sub.+1).sub.2 ] Cl.sup.- • (HCl).sub.x

wherein n is 15 to 17 and s is 1 to 4, x is 0 or
 1. 7. Compoundsaccording to claim 6, wherein s is 2 to
 4. 8. Quaternary higherdi-n-alkyl lower di-alkyl phosphonium chlorides having the formula:

    {[CH.sub.3 (CH.sub.2).sub.m ].sub.2 P.sup.+(C.sub.s H.sub.2s.sub.+1).sub.2 } Cl.sup.- • (HCl).sub.x

wherein m is 8 to 10, s is 1 to
 4. 9. Compounds according to claim 8wherein s is
 1. 10. Quaternary higher dialkyl lower monoalkyl isobutylphosphonium chlorides having the formula: ##STR6## wherein r is 8 to 30,s is 1 to 4 and x is 0 or
 1. 11. Compounds according to claim 10 whereins is
 2. 12. Didecyl dimethyl phosphonium chloride.
 13. Didodecylisobutyl ethyl phosphonium chloride.
 14. Dioctadecyl diethyl phosphoniumcloride.
 15. A composition according to claim 3 wherein said phosphoniumsalt component has X anions selected from the group consisting ofhalides, phosphtaes, sulfates, sulfonates, tetrafluoroborate, nitrate,and nitrite.
 16. Compounds according to claim 1 wherein x is
 0. 17.Compounds according to claim 1 wherein x is
 1. 18. Dinonyl dimethylphosphonium chloride.
 19. Dihexadecyl isobutyl ethyl phosphoniumchloride.